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EP0155503B1 - Improvement in the dewatering of wet paper webs using mannich acrylamide polymers - Google Patents

Improvement in the dewatering of wet paper webs using mannich acrylamide polymers Download PDF

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Publication number
EP0155503B1
EP0155503B1 EP85101607A EP85101607A EP0155503B1 EP 0155503 B1 EP0155503 B1 EP 0155503B1 EP 85101607 A EP85101607 A EP 85101607A EP 85101607 A EP85101607 A EP 85101607A EP 0155503 B1 EP0155503 B1 EP 0155503B1
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EP
European Patent Office
Prior art keywords
methyl
paper
polymer
radicals
water
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85101607A
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German (de)
French (fr)
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EP0155503A1 (en
Inventor
Robert Emil Scalfarotto
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Wyeth Holdings LLC
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American Cyanamid Co
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Filing date
Publication date
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Priority to AT85101607T priority Critical patent/ATE33050T1/en
Publication of EP0155503A1 publication Critical patent/EP0155503A1/en
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Publication of EP0155503B1 publication Critical patent/EP0155503B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/18—De-watering; Elimination of cooking or pulp-treating liquors from the pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

Definitions

  • Papermaking machines of the Fourdrinier type generally contain three specific zones wherein water is removed from the deposited web of fibers supported on the wire.
  • the first water removal zone is where water is removed by gravity. It is positioned immediately subsequent to the slice of the headbox.
  • the next water- removal zone is the low vacuum drainage zone where a low vacuum is generated by the rapid motion of the wire of the Fourdrinier table over the foils and table rolls thus drawing water from the deposited wet web.
  • the third and final dewatering zone between the first flat boxes and the couch roll is a high vacuum zone where the water is squeezed from within the fiber flocs by the negative vacuum pressure. The wet web at consistencies reading up to 25% leaves the Fourdrinier table wire at this point and is transferred to the press section of the paper machine.
  • the web then moves to the driers or drying cylinders section where the remaining water is completely removed by evaporation.
  • the energy required to operate the driers is the most expensive step in water removal from. the wet web while dewatering on the wire of the Fourdrinier table is the least.
  • the amount of water in the wet paper web leaving the table wire at the couch roll of the Fourdrinier paper machine can be reduced by adding to the aqueous fiber furnish an effective amount of a Mannich acrylamide polymer having a molecular weight not greater than 300,000 and maintaining the pH of the furnish at a value of 5.5 or less, thereby resulting in the expenditure of less energy in the driers wherein the wet web is dried to a water content of about 5% of less.
  • the machine speed thereof can be increased, thereby resulting in an increase in the quantity of paper manufactured without further expenditure of drying energy.
  • the novel process of the present invention comprises an improvement over the prior art process for the production of paper wherein an aqueous slurry of papermaking fibers containing from 0.01 to 0.3 percent solids, by weight, based on the fiber content of the furnish, preferably 0.05-0.15 percent, of a water-soluble, essentially linear polymer having the formula: wherein R is methyl or ethyl, R 1 is hydrogen or methyl, n is an integer of 1-6, the ratio of x:y ranges from 1:4 to 4:1, preferably from 1:3 to 3:1, and z is the degree of polymerization, is wet-laid in a papermaking machine to form paper sheet.
  • the improvement of the present invention comprises the use of polymer having a molecular weight not greater than 300,000 and the maintenance of the pH of the aqueous slurry of papermaking fibers at a value of 5.5 or less, preferably from 4 to 5.
  • R is methyl
  • R 1 is hydrogen
  • the ratio of x:y is 3: 1.
  • the preferred molecular weight ranges from 25,000 to 150,000.
  • the improvement represented by the instant invention although not as effective in water removal at the gravity and low vacuum drainage zones, is more effective at the high vacuum zone of the apparatus to the extent that the overall water removal in the machine is more efficient.
  • the polymers useful in the practice of the process of the present invention may be prepared in accordance with the disclosure of the above-mentioned patent. Salts of these polymers may also be used.
  • the polymers may be added to the aqueous slurry of papermaking fibers, as is known, at any point prior to formation of the web, usually after the beating and refining operations.
  • Alum in amounts of 0.1-2.0% of the slurry may also be added and is, in fact, often preferred.
  • the fibers used to form the papermaking slurry may comprise any known papermaking fibers such as bleached softwood, bleached hardwood, unbleached kraft, mixtures thereof and the like.
  • Comonomers such as acrylic acid, methacrylic acid, 2-aminoethy acrylate, methyl acrylate, acrylonitrile, styrene, vinyl acetate and the like may also be incorporated into the chain of the polymers useful herein and still be within the scope of the present invention. These comonomers may be present in amounts ranging from 5-25%, by weight, of the total polymer.
  • a furnish composition comprising about 1.0% of a 50/50 mixture of bleached softwood/hardwood papermaking fibers, 0.25% of alum, and 10% of amorphous silica filler and having a pH of 4.7-4.8, are added, as 0.05 solids, a series of polymers containing 75% dimethylaminomethylacrylamide radicals and 25% acrylamide radical of varying molecular weights.
  • the resultant slurry is dewatered on the Vacuum Water Release Analyzer to obtain the Similated Couch Consistency or Percent Dry/Wet Ratio (S.C.C.) after low vacuum drainage and high vacuum dewatering.
  • the value expressed is an average of 10 tests.
  • Table I The results are set forth in Table I below.
  • Example 2 The procedure of Example 1 is again followed except that the pH of the slurry is 5.5. The results are set forth in Table II, below.
  • Example 1 The procedure of Example 1 is again followed except that the concentration of alum is increased to 0.5% and the amorphous silica is eliminated. The pH is 4.5. The results are set forth in Table III, below.
  • Example 1 The procedure of Example 1 is again followed except that the pH is increased to 6.4.
  • the results are set forth in Table IV, below.
  • Example 1 The procedure of Example 1 is again followed except that the pH is 7.8 and higher molecular weight polymer is employed. Table VII, below, set forth the results recorded.
  • Example 1 The procedure of Example 1 is again followed except that the fibers in the slurry comprise a mixture (90/10) of unblecahed kraft and recycled waste paper fibers.
  • the alum concentration is 0.9%
  • the filler is omitted
  • 0.15% of rosin size is added and the pH is 4.5.
  • Table VIII The results are set forth in Table VIII, below.
  • Example 7 The procedure of Example 7 is again followed except that the pH is 6.0. Results are recorded in Table IX, below.
  • Example 1 The procedure of Example 1 is again followed except that the pH is 4.3-4.5. Testing results are set forth in Table XIII, below.
  • Example 1 The procedure of Example 1 is again followed except that the dimethylaminomethylacrylamide radicals are replaced by diethylaminomethyl acrylamide radicals. Again, excellent results are achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Materials For Medical Uses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

@ Dewatering of wet paper webs in general and particularly under high vacuum is improved by the addition of a Mannich acrylamide polymer having a molecular weight of not greater than about 300,000 to an aqueous slurry of paper-making fibers having a pH less than about 5.5.

Description

    Background of the invention
  • In the process of making paper wherein a fiber furnish is introduced at the inlet side of a conventional papermaking machine, such as a Fourdrinier machine, it has become the accepted procedure to add polymeric materials to the furnish in order to improve the drainage rate of the furnish on the machine. Generally, it was preferred to utilize high molecular weight materials for this purpose because the higher molecular weight materials have proven to be more successful flocculants in other flocculation procedures. U.S. Patent 3,323,979 is exemplary of the prior art in this area. This patent teaches the use of Mannich acrylamide polymers having molecular weights over 1,000,000 to increase the drainage rate of the furnish when preparing paper. U.S. Patent Nos. 4093542 and 4113685 relate to the use of polymeric Mannich bases having molecular weights exceeding preferably 100,000 as flocculating agents.
  • Papermaking machines of the Fourdrinier type generally contain three specific zones wherein water is removed from the deposited web of fibers supported on the wire. The first water removal zone is where water is removed by gravity. It is positioned immediately subsequent to the slice of the headbox. The next water- removal zone is the low vacuum drainage zone where a low vacuum is generated by the rapid motion of the wire of the Fourdrinier table over the foils and table rolls thus drawing water from the deposited wet web. The third and final dewatering zone between the first flat boxes and the couch roll is a high vacuum zone where the water is squeezed from within the fiber flocs by the negative vacuum pressure. The wet web at consistencies reading up to 25% leaves the Fourdrinier table wire at this point and is transferred to the press section of the paper machine. The web then moves to the driers or drying cylinders section where the remaining water is completely removed by evaporation. The energy required to operate the driers is the most expensive step in water removal from. the wet web while dewatering on the wire of the Fourdrinier table is the least.
  • Attempts to reduce the amount of water present in the paper web introduced into the driers have been ongoing, and continue to be ongoing, since the costs of energy continue to rise. Therefore, if the removal of water from the wet paper web entering the driers in the papermaking process could be reduced, a long-felt need in the industry would be satisfied.
    • Summary of the invention
  • It has now been found that the amount of water in the wet paper web leaving the table wire at the couch roll of the Fourdrinier paper machine can be reduced by adding to the aqueous fiber furnish an effective amount of a Mannich acrylamide polymer having a molecular weight not greater than 300,000 and maintaining the pH of the furnish at a value of 5.5 or less, thereby resulting in the expenditure of less energy in the driers wherein the wet web is dried to a water content of about 5% of less. Alternatively, since the wet web is dried upon exitting the couch roll of the papermaking machine, the machine speed thereof can be increased, thereby resulting in an increase in the quantity of paper manufactured without further expenditure of drying energy.
    • Description of the invention including preferred embodiments
  • The novel process of the present invention comprises an improvement over the prior art process for the production of paper wherein an aqueous slurry of papermaking fibers containing from 0.01 to 0.3 percent solids, by weight, based on the fiber content of the furnish, preferably 0.05-0.15 percent, of a water-soluble, essentially linear polymer having the formula:
    Figure imgb0001
    wherein R is methyl or ethyl, R1 is hydrogen or methyl, n is an integer of 1-6, the ratio of x:y ranges from 1:4 to 4:1, preferably from 1:3 to 3:1, and z is the degree of polymerization, is wet-laid in a papermaking machine to form paper sheet. The improvement of the present invention comprises the use of polymer having a molecular weight not greater than 300,000 and the maintenance of the pH of the aqueous slurry of papermaking fibers at a value of 5.5 or less, preferably from 4 to 5. In a preferred embodiment, R is methyl, R1 is hydrogen, and the ratio of x:y is 3: 1. The preferred molecular weight ranges from 25,000 to 150,000.
  • The above-mentioned .U.S. Patent 3,323,979 describes the use of the same polymer as specified above with regard to its structure but having a molecular weight of at least about one million. The use of such a polymer as a drainage aid in the papermaking machine of the papermaking process results in the very effective removal of water at the gravity drainage and low vacuum zones of the papermaking machine, i.e. Fourdrinier machine, because the high molecular weight of the polymer causes the formation of large flocs of the fibers. Once the fibers are positioned on the wire, however, large spaces appear between the flocked fibers. These large spaces enable the rapid removal of water in the gravity and low vacuum drainage zones. Unfortunately, these large spaces are a detriment to the removal of water in the high vacuum dewatering zone of the apparatus because air is sucked through these spaces rather than impinging and pressing upon the flocked paper fibers. Therefore, water removal in the latter stage of zone of the apparatus is not as effective as one would desire.
  • The improvement represented by the instant invention, although not as effective in water removal at the gravity and low vacuum drainage zones, is more effective at the high vacuum zone of the apparatus to the extent that the overall water removal in the machine is more efficient.
  • The polymers useful in the practice of the process of the present invention may be prepared in accordance with the disclosure of the above-mentioned patent. Salts of these polymers may also be used. The polymers may be added to the aqueous slurry of papermaking fibers, as is known, at any point prior to formation of the web, usually after the beating and refining operations.
  • Alum in amounts of 0.1-2.0% of the slurry may also be added and is, in fact, often preferred.
  • The fibers used to form the papermaking slurry may comprise any known papermaking fibers such as bleached softwood, bleached hardwood, unbleached kraft, mixtures thereof and the like.
  • Comonomers such as acrylic acid, methacrylic acid, 2-aminoethy acrylate, methyl acrylate, acrylonitrile, styrene, vinyl acetate and the like may also be incorporated into the chain of the polymers useful herein and still be within the scope of the present invention. These comonomers may be present in amounts ranging from 5-25%, by weight, of the total polymer.
  • The following examples are set forth for purposes of illustration only and are not to be construed as limitations on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless expressed otherwise.
  • The Simulated Couch Consistency of Percent Dry/Wet Ratio values expressed in the following examples were ascertained using a PRM Vacuum Water Release Analyzer developed and distributed by Paper Research Materials Co., 770 James St., Apt. 1206, Syracuse, N.Y.
    • Example 1
  • To a furnish composition comprising about 1.0% of a 50/50 mixture of bleached softwood/hardwood papermaking fibers, 0.25% of alum, and 10% of amorphous silica filler and having a pH of 4.7-4.8, are added, as 0.05 solids, a series of polymers containing 75% dimethylaminomethylacrylamide radicals and 25% acrylamide radical of varying molecular weights. The resultant slurry is dewatered on the Vacuum Water Release Analyzer to obtain the Similated Couch Consistency or Percent Dry/Wet Ratio (S.C.C.) after low vacuum drainage and high vacuum dewatering. The value expressed is an average of 10 tests. The results are set forth in Table I below.
    Figure imgb0002
    • Example 2
  • The procedure of Example 1 is again followed except that the pH of the slurry is 5.5. The results are set forth in Table II, below.
    Figure imgb0003
    • Example 3
  • The procedure of Example 1 is again followed except that the concentration of alum is increased to 0.5% and the amorphous silica is eliminated. The pH is 4.5. The results are set forth in Table III, below.
  • Figure imgb0004
    • Example 4 (Comparative)
  • The procedure of Example 1 is again followed except that the pH is increased to 6.4. The results are set forth in Table IV, below.
    Figure imgb0005
    • Example 5 (Comparative)
  • Again following the procedure of Example 1 except that the filler comprises 15% of calcium carbonate and the pH is 7.2-7.5, the results set forth in Table V, below, are recorded.
    Figure imgb0006
    • Example 6 (Comparative)
  • When following the procedure of Example 1 except that the pH is 7.6, the results set forth in Table VI, below, are recorded.
    Figure imgb0007
    • Example 7 (Comparative)
  • The procedure of Example 1 is again followed except that the pH is 7.8 and higher molecular weight polymer is employed. Table VII, below, set forth the results recorded.
    Figure imgb0008
    • Example 8
  • The procedure of Example 1 is again followed except that the fibers in the slurry comprise a mixture (90/10) of unblecahed kraft and recycled waste paper fibers. The alum concentration is 0.9%, the filler is omitted, 0.15% of rosin size is added and the pH is 4.5. The results are set forth in Table VIII, below.
    Figure imgb0009
    • Example 9 (Comparative)
  • The procedure of Example 7 is again followed except that the pH is 6.0. Results are recorded in Table IX, below.
    Figure imgb0010
    • Example 10
  • Again following the procedure of Example 8 except that the fibers are 100% unbleached kraft, the alum concentration is reduced to 0.5% and the rosin size is replaced by 6% black liquor solids, the results set forth in Table X are observed.
    Figure imgb0011
    • Example 11 (Comparative)
  • When the procedure of Example X is again followed except that the pH is 6.0, the results set forth in Table XI are obtained.
    Figure imgb0012
    • Example 12
  • A slurry containing 100% unbleached kraft fibers, 0.5% alum, 1.0% amorphous silica, and 6.0% black liquor solids at a pH of 4.5 is treated and tested as in Example 1. The results are set forth in Table XII, below.
    Figure imgb0013
    • Example 13
  • The procedure of Example 1 is again followed except that the pH is 4.3-4.5. Testing results are set forth in Table XIII, below.
    Figure imgb0014
    • Example 14
  • When the procedure of Example 1 is again followed except that the dimethylaminomethyl acrylamide radicals of the polymer are replaced by dimethyl(aminohexyl acrylamide) radicals, similar results are achieved.
    • Example 15
  • The procedure of Example 1 is again followed except that the dimethylaminomethylacrylamide radicals are replaced by diethylaminomethyl acrylamide radicals. Again, excellent results are achieved.

Claims (7)

1. In a method for the production of paper wherein an aqueous slurry of paper-producing fibers containing from 0.01 to 0.3 percent,solids, by weight, based on the fiber content of the furnish, of a water-soluble, essentially linear, polymer having the formula:
Figure imgb0015
wherein R is methyl or ethyl, R1 is hydrogen or methyl, n is an integer or 1-6, the ratio of x:y ranges from 1:4 to 4:1, and z is the degree of polymerization, whereby optionally comonomers of acrylic acid, methacrylic acid, 2-aminoethylacrylate, methylacrylate, acrylonitrile, styrene or vinyl acetate are present in the chain of the polymer in amounts ranging from 5 to 25 percent by weight of the total polymer, is wet-laid to form paper, characterized in that z is such that the molecular weight of the polymer is not greater than 300,000 and the pH of the slurry is 5.5 or less.
2. A method according to Claim 1 wherein both R radicals are methyl.
3. A method according to Claim 1 wherein n is 1.
4. A method according to Claim 1 wherein n is 1 and both R radicals are methyl.
5. A method according to Claim 1 wherein n is 1, both R radicals are methyl and R1 is hydrogen.
6. A method according to Claim 1 wherein n is 1, both R radicals are methyl, R1 is hydrogen and the ratio of x:y is 3:1.
7. A method according to Claim 1 wherein the pH is from 4-5.
EP85101607A 1984-03-26 1985-02-14 Improvement in the dewatering of wet paper webs using mannich acrylamide polymers Expired EP0155503B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85101607T ATE33050T1 (en) 1984-03-26 1985-02-14 DEWATERING OF WET PAPER WEBS BY APPLICATION OF POLYMERIC MANNICH ACRYLAMIDES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/593,053 US4599139A (en) 1984-03-26 1984-03-26 Dewatering of wet paper webs using Mannich acrylamide polymers
US593053 1984-03-26

Publications (2)

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EP0155503A1 EP0155503A1 (en) 1985-09-25
EP0155503B1 true EP0155503B1 (en) 1988-03-16

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US (1) US4599139A (en)
EP (1) EP0155503B1 (en)
JP (1) JPS60209096A (en)
KR (1) KR850006456A (en)
AT (1) ATE33050T1 (en)
AU (1) AU563874B2 (en)
DE (1) DE3561896D1 (en)
ES (1) ES541550A0 (en)
NO (1) NO851190L (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5228692A (en) * 1991-08-23 1993-07-20 Innovative Environmental Tech., Inc. Gaming form

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3323979A (en) * 1964-09-24 1967-06-06 Dow Chemical Co Method of improving the drainage rate in forming paper by incorporating a reaction product of polyacrylamide, formaldehyde and dialkylamine in the furnish
US3874994A (en) * 1971-12-23 1975-04-01 American Cyanamid Co Process of making paper where an ionic vinylamide polymer latex is added to the furnish to improve dry strength of the paper
US4093542A (en) * 1973-07-04 1978-06-06 Chemische Fabrik Stockhausen & Cie Flocculating agent comprising water-in-oil emulsion of H-active polymer carrying formaldehyde and amine radicals
US4113685A (en) * 1975-01-02 1978-09-12 Chemische Fabrik Stockhausen & Cie Flocculating agent comprising water-in-oil emulsion of stabilizer plus NH-active polymer carrying formaldehyde and amine radicals

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AU4031785A (en) 1985-10-03
ES8603609A1 (en) 1986-01-01
JPS60209096A (en) 1985-10-21
KR850006456A (en) 1985-10-05
ES541550A0 (en) 1986-01-01
DE3561896D1 (en) 1988-04-21
US4599139A (en) 1986-07-08
AU563874B2 (en) 1987-07-23
ATE33050T1 (en) 1988-04-15
EP0155503A1 (en) 1985-09-25
NO851190L (en) 1985-09-27

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